CA2751825A1 - Casting resin system for insulating materials in switch gears - Google Patents
Casting resin system for insulating materials in switch gears Download PDFInfo
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- CA2751825A1 CA2751825A1 CA2751825A CA2751825A CA2751825A1 CA 2751825 A1 CA2751825 A1 CA 2751825A1 CA 2751825 A CA2751825 A CA 2751825A CA 2751825 A CA2751825 A CA 2751825A CA 2751825 A1 CA2751825 A1 CA 2751825A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Insulating Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to an insulating resin for switch gears on the basis of glycidyl ester, comprising methyl nadic anhydride/hydrogenated methyl nadic anhydride as hardener and an N-substituted imidazole as accelerator. Furthermore, plate-shaped aluminum oxide is added as filler. The resin has a substantially elevated glass transition temperature, while at the same time having a high mechanical level and being very tracking resistant. It is suitable as a casting resin in GIL systems.
Description
Description Casting resin system for insulating materials in switch gears The present invention relates to the field of insulating resins for switchgear, especially to those insulating resins used as casting resins for "gas-insulated lines" (GILs).
In electrical switchgear - especially in the case of compact design - the insulating composition plays an important role.
In these insulating resins, which are usually used in the form of casting resins, a high glass transition temperature is advantageous, but at the same time there frequently also exist high demands on favorable mechanical properties, high field strength and good tracking characteristics. Especially in the case of GILs, the tracking characteristics are often a crucial parameter; further requirements are high burst values and - if possible - a good resistance to decomposition products of gases such as SF6.
It is thus an object of the present invention to provide, as an alternative to the existing solutions, an insulating resin for switchgear, in which an increased glass transition temperature is discovered with, at the same time, good or even improved other properties, especially with regard to the tracking resistance.
This object is achieved by an insulating resin according to claim 1 of the present application. Accordingly, an insulating resin based on glycidyl esters for insulating compositions in switchgear is proposed, formed from the starting components comprising:
a) a material comprising methylnadic anhydride and/or hydrogenated methylnadic anhydride, PCT/EP2010/050682 - la -b) a material comprising an imidazole of the following structure:
N
N
where Rl is selected from the group comprising alkyl, long-chain alkyl, alkenyl, cycloalkyl, haloalkyl, aryl;
R2, R3, R4 are each independently selected from the group comprising hydrogen, alkyl, long-chain alkyl, alkenyl, cycloalkyl, haloalkyl, aryl, where one or more nonadjacent CH2 groups in suitable radicals may each independently be replaced by -0-, -S-, -NH-, -NR -, -SiR R -, -CO-, -COO-, -OCO-, -OCO-O-, -SO2-, CN, -S-CO-, -CO-S-, -CY1=CY2- or -C=C-, specifically in such a way that oxygen and/or sulfur atoms are not bonded directly to one another, and are likewise optionally replaced by aryl or heteroaryl preferably containing 1 to 30 carbon atoms (terminal CH3 groups are understood like CH2 groups in the sense of CH2-H, R and R = alkyl) c) a filler comprising alumina flakes.
General group definition: within the description and the claims, general groups, for example alkyl, alkoxy, aryl, etc., are claimed and described. Unless stated otherwise, preference is given to using the following groups among the groups described in general terms in the context of the present invention:
PCT/EP2010/050682 - 2a -alkyl: linear and branched Cl-C8-alkyls, long-chain alkyls: linear and branched C5-C20-alkyls alkenyl: C2-C6-alkenyl; cycloalkyl: C3-C8-cycloalkyl;
alkylene: selected from the group comprising methylene; 1,1-ethylene; 1,2-ethylene; 1,1-propylidene; 1,2-propylene; 1,3-propylene; 2,2-propylidene; butan-2-ol-1,4-diyl; propan-2-ol-1,3-diyl; 1,4-butylene; cyclohexane-1,1-diyl; cyclohexane-1,2-diyl; cyclohexane-1,3-diyl; cyclohexane-1,4-diyl; cyclopentane-1,1-diyl; cyclopentane-1,2-diyl; and cyclopentane-1,3-diyl, vinyl, cyanoethyl, undecyl, hydroxymethyl aryl: selected from aromatics with a molecular weight below 300 Da haloalkyl: selected from the group comprising mono-, di-, tri-, poly- and perhalogenated linear and branched C1-C8-alkyl.
Unless defined differently, the following groups are more preferred groups among the general group definitions:
alkyl: linear and branched C1-C6-alkyl, especially methyl, ethyl, propyl, isopropyl;
aryl: selected from the group comprising: phenyl; biphenyl;
naphthalenyl; anthracenyl; phenanthrenyl, benzyl.
It has been found that, surprisingly, in the presence of the two components, a kind of synergistic effect in many applications of the present invention makes it possible to obtain insulating resins which have a greatly increased glass transition temperature compared to the existing solutions with, at the same time, very high other properties such as tracking resistance or burst value.
In the context of the present invention, the term "insulating resin" comprises and/or includes especially a (preferably low-viscosity) casting resin system based on epoxy resin and anhydride component with controlled reactivity.
In the context of the present invention, the term "switchgear"
comprises and/or includes especially assemblies for low, moderate and high voltage.
In the context of the present invention, the term "based on glycidyl esters" comprises and/or includes especially the fact that glycidyl ester resin is used as one starting component -especially main component. It is possible to use all resins known in the prior art.
In the context of the present invention, the term "formed from the starting component(s)" means and/or comprises especially the fact that the insulating resin is produced from this/these component(s).
In the context of the present invention, the term "methylnadic anhydride" means and/or comprises especially the following compound:
Me In the context of the present invention, the term "alumina"
means and/or comprises especially a material which consists to an extent of >_95% (% by weight), preferably ?98% and most preferably of >_99% of alumina.
PCT/EP2010/050682 - 4a -In a preferred embodiment of the present invention, the ratio of material a) to material b) (in weight/weight) is from >_50:1 to :_300:1. This has been found to be advantageous in practice since the glass transition temperature can thus often be increased once again.
The ratio of material a) to material b) (in weight/weight) is preferably from >_100:1 to :_250:1, more preferably >_150:1 to :_220:1.
In a preferred embodiment of the present invention, the proportion of material a) in the resin (in weight/weight based on glycidyl esters) is from >_0.8:1 to :_1:1. This too has often been found to be advantageous for the increase in the glass transition temperature.
The ratio of material a) to material b) in the resin (in weight/weight based on glycidyl esters) is preferably from >_0.85:1 to :_0.98:1, more preferably >_0.92 to :_0.97:1.
In a preferred embodiment of the present invention, the proportion of material b) in the resin (in weight/weight based on glycidyl esters) is from >_0.01:1 to :_0.1:1, more preferably >_0.02:1 to :_0.09:1 and most preferably 0.04:1 to :50.07:1.
In a preferred embodiment of the present invention, component b) is selected from the group comprising 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-isopropylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-ethylimidazole, imidazole, 1-benzyl-2-phenylimidazole, 1-vinylimidazole, 2-methylimidazole, 2-heptadecylimidazole, and mixtures thereof.
In a preferred embodiment of the present invention, the proportion of the filler c) in the resin (in weight/weight of the overall mixture) is from ?50% to -100%. Preference is given to ?65%, more preference to ?70%.
In a preferred embodiment of the present invention, the d50 of the filler c) is from ?2 pm to <6 pm.
This has been found to be useful in practice, since the burst resistance can thus often be increased once again. More preferred is ?3 pm to ~5 pm.
In a preferred embodiment of the present invention, the insulating resin is produced in a curing process comprising a curing step at >_140 C, preferably >_150 C and a curing time of >_12 h, preferably >_14 h and most preferably >_16 h.
The potting operation is preferably under reduced pressure.
The present invention also relates to an insulating part comprising an insulating resin according to the present invention. The insulating part is preferably part of a GIL
system.
The present invention also relates to the use of a resin system based on glycidyl esters, formed from the starting components comprising:
a) a material comprising methylnadic anhydride and/or hydrogenated methylnadic anhydride, b) a material comprising an imidazole of the following structure:
R' N R
N
:(-where Ri is selected from the group comprising alkyl, long-chain alkyl, alkenyl, cycloalkyl, haloalkyl, aryl;
R2, R3, R4 are each independently selected from the group comprising hydrogen, alkyl, long-chain alkyl, alkenyl, cycloalkyl, haloalkyl, aryl, where one or more nonadjacent CH2 groups in suitable radicals may each independently be replaced by -0-, -S-, -NH-, -NR -, -SiR RO -, -CO-, -COO-, -OCO-, -OCO-0-, -S02-, -S-CO-, -CO-S-, -CY1=CY2- or -C=C-, specifically in such a way that oxygen and/or sulfur atoms are not bonded directly to one another, and are likewise optionally replaced by aryl or heteroaryl preferably containing 1 to 30 carbon atoms (terminal CH3 groups are understood like CH2 groups in the sense of CH2-H, R and RO = alkyl) c) a filler comprising alumina flakes as an insulating system for switchgear.
The aforementioned components, and those claimed and those to be used in accordance with the invention which are described in the working examples, are not subject to any particular exceptional conditions in their size, shape configuration, material selection and technical design, and so the selection criteria known in the field of use can be applied without restriction.
Further details, features and advantages of the subject matter of the invention are evident from the dependent claims, and from the description of the accompanying examples which follows.
EXAMPLE I
The present invention is - in a purely illustrative and nonrestrictive manner - examined using the present inventive example I. This involved producing a resin formed from the following components:
Component Rel. proportion by weight glycidyl ester resin 100 methylnadic anhydride 95 1-methylimidazole 0.5 alumina flakes, d50 = 4 pm 70 (based on the overall mixture) The resin was cured at 80 C for 2 h, then at 100 C for 2 h, subsequently at 130 C for 1 h and finally at 150 C for 16 h.
In addition, three (noninventive) comparative resins were prepared.
Comparative example I:
In comparative example I, the filler used was dolomite with a d50 of 21 pm instead of alumina. The preparation conditions were otherwise the same.
Comparative example II:
In comparative example II, the filler used was alumina beads with a d50 of 5 pm instead of alumina flakes. The preparation conditions were otherwise the same.
Comparative example III:
In comparative example III, the filler used was high-grade corundum with a d50 of 4 um instead of alumina flakes. The preparation conditions were otherwise the same.
In a test, firstly, the tensile strength [ISO 527-4], the Martens temperature and the burst value (pressure test with water) were determined.
Resin Tensile Martens Burst value strength ( C) Comparative example 50 N/mm2 139 missed target value I
Comparative example 50 N/mm2 140 missed target value II
Comparative example 70 N/mm2 140 hit target value III
Example I 80 N/mm2 150 hit target value The inventive resin system thus has the highest tensile strength, the highest Martens temperature and meets (with comparative example III) the burst value requirements.
The tracking characteristics of all resin systems were likewise studied; all resins were found to be adequate.
In addition, stability to decomposition products of SF6 [storage over 3 months in highly decomposed SF6] was found.
Here, good stabilities were found only for comparative example I and example I. For the rest of the variants, the stability was reduced, in some cases considerably.
The advantageous properties of the inventive insulating resin are thus seen, it being the only one to meet all requirements.
In electrical switchgear - especially in the case of compact design - the insulating composition plays an important role.
In these insulating resins, which are usually used in the form of casting resins, a high glass transition temperature is advantageous, but at the same time there frequently also exist high demands on favorable mechanical properties, high field strength and good tracking characteristics. Especially in the case of GILs, the tracking characteristics are often a crucial parameter; further requirements are high burst values and - if possible - a good resistance to decomposition products of gases such as SF6.
It is thus an object of the present invention to provide, as an alternative to the existing solutions, an insulating resin for switchgear, in which an increased glass transition temperature is discovered with, at the same time, good or even improved other properties, especially with regard to the tracking resistance.
This object is achieved by an insulating resin according to claim 1 of the present application. Accordingly, an insulating resin based on glycidyl esters for insulating compositions in switchgear is proposed, formed from the starting components comprising:
a) a material comprising methylnadic anhydride and/or hydrogenated methylnadic anhydride, PCT/EP2010/050682 - la -b) a material comprising an imidazole of the following structure:
N
N
where Rl is selected from the group comprising alkyl, long-chain alkyl, alkenyl, cycloalkyl, haloalkyl, aryl;
R2, R3, R4 are each independently selected from the group comprising hydrogen, alkyl, long-chain alkyl, alkenyl, cycloalkyl, haloalkyl, aryl, where one or more nonadjacent CH2 groups in suitable radicals may each independently be replaced by -0-, -S-, -NH-, -NR -, -SiR R -, -CO-, -COO-, -OCO-, -OCO-O-, -SO2-, CN, -S-CO-, -CO-S-, -CY1=CY2- or -C=C-, specifically in such a way that oxygen and/or sulfur atoms are not bonded directly to one another, and are likewise optionally replaced by aryl or heteroaryl preferably containing 1 to 30 carbon atoms (terminal CH3 groups are understood like CH2 groups in the sense of CH2-H, R and R = alkyl) c) a filler comprising alumina flakes.
General group definition: within the description and the claims, general groups, for example alkyl, alkoxy, aryl, etc., are claimed and described. Unless stated otherwise, preference is given to using the following groups among the groups described in general terms in the context of the present invention:
PCT/EP2010/050682 - 2a -alkyl: linear and branched Cl-C8-alkyls, long-chain alkyls: linear and branched C5-C20-alkyls alkenyl: C2-C6-alkenyl; cycloalkyl: C3-C8-cycloalkyl;
alkylene: selected from the group comprising methylene; 1,1-ethylene; 1,2-ethylene; 1,1-propylidene; 1,2-propylene; 1,3-propylene; 2,2-propylidene; butan-2-ol-1,4-diyl; propan-2-ol-1,3-diyl; 1,4-butylene; cyclohexane-1,1-diyl; cyclohexane-1,2-diyl; cyclohexane-1,3-diyl; cyclohexane-1,4-diyl; cyclopentane-1,1-diyl; cyclopentane-1,2-diyl; and cyclopentane-1,3-diyl, vinyl, cyanoethyl, undecyl, hydroxymethyl aryl: selected from aromatics with a molecular weight below 300 Da haloalkyl: selected from the group comprising mono-, di-, tri-, poly- and perhalogenated linear and branched C1-C8-alkyl.
Unless defined differently, the following groups are more preferred groups among the general group definitions:
alkyl: linear and branched C1-C6-alkyl, especially methyl, ethyl, propyl, isopropyl;
aryl: selected from the group comprising: phenyl; biphenyl;
naphthalenyl; anthracenyl; phenanthrenyl, benzyl.
It has been found that, surprisingly, in the presence of the two components, a kind of synergistic effect in many applications of the present invention makes it possible to obtain insulating resins which have a greatly increased glass transition temperature compared to the existing solutions with, at the same time, very high other properties such as tracking resistance or burst value.
In the context of the present invention, the term "insulating resin" comprises and/or includes especially a (preferably low-viscosity) casting resin system based on epoxy resin and anhydride component with controlled reactivity.
In the context of the present invention, the term "switchgear"
comprises and/or includes especially assemblies for low, moderate and high voltage.
In the context of the present invention, the term "based on glycidyl esters" comprises and/or includes especially the fact that glycidyl ester resin is used as one starting component -especially main component. It is possible to use all resins known in the prior art.
In the context of the present invention, the term "formed from the starting component(s)" means and/or comprises especially the fact that the insulating resin is produced from this/these component(s).
In the context of the present invention, the term "methylnadic anhydride" means and/or comprises especially the following compound:
Me In the context of the present invention, the term "alumina"
means and/or comprises especially a material which consists to an extent of >_95% (% by weight), preferably ?98% and most preferably of >_99% of alumina.
PCT/EP2010/050682 - 4a -In a preferred embodiment of the present invention, the ratio of material a) to material b) (in weight/weight) is from >_50:1 to :_300:1. This has been found to be advantageous in practice since the glass transition temperature can thus often be increased once again.
The ratio of material a) to material b) (in weight/weight) is preferably from >_100:1 to :_250:1, more preferably >_150:1 to :_220:1.
In a preferred embodiment of the present invention, the proportion of material a) in the resin (in weight/weight based on glycidyl esters) is from >_0.8:1 to :_1:1. This too has often been found to be advantageous for the increase in the glass transition temperature.
The ratio of material a) to material b) in the resin (in weight/weight based on glycidyl esters) is preferably from >_0.85:1 to :_0.98:1, more preferably >_0.92 to :_0.97:1.
In a preferred embodiment of the present invention, the proportion of material b) in the resin (in weight/weight based on glycidyl esters) is from >_0.01:1 to :_0.1:1, more preferably >_0.02:1 to :_0.09:1 and most preferably 0.04:1 to :50.07:1.
In a preferred embodiment of the present invention, component b) is selected from the group comprising 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-isopropylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-ethylimidazole, imidazole, 1-benzyl-2-phenylimidazole, 1-vinylimidazole, 2-methylimidazole, 2-heptadecylimidazole, and mixtures thereof.
In a preferred embodiment of the present invention, the proportion of the filler c) in the resin (in weight/weight of the overall mixture) is from ?50% to -100%. Preference is given to ?65%, more preference to ?70%.
In a preferred embodiment of the present invention, the d50 of the filler c) is from ?2 pm to <6 pm.
This has been found to be useful in practice, since the burst resistance can thus often be increased once again. More preferred is ?3 pm to ~5 pm.
In a preferred embodiment of the present invention, the insulating resin is produced in a curing process comprising a curing step at >_140 C, preferably >_150 C and a curing time of >_12 h, preferably >_14 h and most preferably >_16 h.
The potting operation is preferably under reduced pressure.
The present invention also relates to an insulating part comprising an insulating resin according to the present invention. The insulating part is preferably part of a GIL
system.
The present invention also relates to the use of a resin system based on glycidyl esters, formed from the starting components comprising:
a) a material comprising methylnadic anhydride and/or hydrogenated methylnadic anhydride, b) a material comprising an imidazole of the following structure:
R' N R
N
:(-where Ri is selected from the group comprising alkyl, long-chain alkyl, alkenyl, cycloalkyl, haloalkyl, aryl;
R2, R3, R4 are each independently selected from the group comprising hydrogen, alkyl, long-chain alkyl, alkenyl, cycloalkyl, haloalkyl, aryl, where one or more nonadjacent CH2 groups in suitable radicals may each independently be replaced by -0-, -S-, -NH-, -NR -, -SiR RO -, -CO-, -COO-, -OCO-, -OCO-0-, -S02-, -S-CO-, -CO-S-, -CY1=CY2- or -C=C-, specifically in such a way that oxygen and/or sulfur atoms are not bonded directly to one another, and are likewise optionally replaced by aryl or heteroaryl preferably containing 1 to 30 carbon atoms (terminal CH3 groups are understood like CH2 groups in the sense of CH2-H, R and RO = alkyl) c) a filler comprising alumina flakes as an insulating system for switchgear.
The aforementioned components, and those claimed and those to be used in accordance with the invention which are described in the working examples, are not subject to any particular exceptional conditions in their size, shape configuration, material selection and technical design, and so the selection criteria known in the field of use can be applied without restriction.
Further details, features and advantages of the subject matter of the invention are evident from the dependent claims, and from the description of the accompanying examples which follows.
EXAMPLE I
The present invention is - in a purely illustrative and nonrestrictive manner - examined using the present inventive example I. This involved producing a resin formed from the following components:
Component Rel. proportion by weight glycidyl ester resin 100 methylnadic anhydride 95 1-methylimidazole 0.5 alumina flakes, d50 = 4 pm 70 (based on the overall mixture) The resin was cured at 80 C for 2 h, then at 100 C for 2 h, subsequently at 130 C for 1 h and finally at 150 C for 16 h.
In addition, three (noninventive) comparative resins were prepared.
Comparative example I:
In comparative example I, the filler used was dolomite with a d50 of 21 pm instead of alumina. The preparation conditions were otherwise the same.
Comparative example II:
In comparative example II, the filler used was alumina beads with a d50 of 5 pm instead of alumina flakes. The preparation conditions were otherwise the same.
Comparative example III:
In comparative example III, the filler used was high-grade corundum with a d50 of 4 um instead of alumina flakes. The preparation conditions were otherwise the same.
In a test, firstly, the tensile strength [ISO 527-4], the Martens temperature and the burst value (pressure test with water) were determined.
Resin Tensile Martens Burst value strength ( C) Comparative example 50 N/mm2 139 missed target value I
Comparative example 50 N/mm2 140 missed target value II
Comparative example 70 N/mm2 140 hit target value III
Example I 80 N/mm2 150 hit target value The inventive resin system thus has the highest tensile strength, the highest Martens temperature and meets (with comparative example III) the burst value requirements.
The tracking characteristics of all resin systems were likewise studied; all resins were found to be adequate.
In addition, stability to decomposition products of SF6 [storage over 3 months in highly decomposed SF6] was found.
Here, good stabilities were found only for comparative example I and example I. For the rest of the variants, the stability was reduced, in some cases considerably.
The advantageous properties of the inventive insulating resin are thus seen, it being the only one to meet all requirements.
Claims (9)
1. An insulating resin for insulating compositions in switchgear based on glycidyl esters, formed from the starting components comprising:
a) a material comprising methylnadic anhydride and/or hydrogenated methylnadic anhydride, b) a material comprising an imidazole of the following structure:
where R1 is selected from the group comprising alkyl, long-chain alkyl, alkenyl, cycloalkyl, haloalkyl, aryl;
R2, R3, R4 are each independently selected from the group comprising hydrogen, alkyl, long-chain alkyl, alkenyl, cycloalkyl, haloalkyl, aryl, where one or more nonadjacent CH2 groups in suitable radicals may each independently be replaced by -O-, -S-, -NH-, -NR~-, -SiR~R~~-, -CO-, -COO-, -OCO-, -OCO-O-, -SO2-, -S-CO-, -CO-S-, -CY1=CY2- or -C.ident.C-, specifically in such a way that oxygen and/or sulfur atoms are not bonded directly to one another, and are likewise optionally replaced by aryl or heteroaryl preferably containing 1 to 30 carbon atoms (terminal CH3 groups are -10a-understood like CH2 groups in the sense of CH2-H, R~ and R~~ = alkyl), c) a filler comprising alumina flakes.
a) a material comprising methylnadic anhydride and/or hydrogenated methylnadic anhydride, b) a material comprising an imidazole of the following structure:
where R1 is selected from the group comprising alkyl, long-chain alkyl, alkenyl, cycloalkyl, haloalkyl, aryl;
R2, R3, R4 are each independently selected from the group comprising hydrogen, alkyl, long-chain alkyl, alkenyl, cycloalkyl, haloalkyl, aryl, where one or more nonadjacent CH2 groups in suitable radicals may each independently be replaced by -O-, -S-, -NH-, -NR~-, -SiR~R~~-, -CO-, -COO-, -OCO-, -OCO-O-, -SO2-, -S-CO-, -CO-S-, -CY1=CY2- or -C.ident.C-, specifically in such a way that oxygen and/or sulfur atoms are not bonded directly to one another, and are likewise optionally replaced by aryl or heteroaryl preferably containing 1 to 30 carbon atoms (terminal CH3 groups are -10a-understood like CH2 groups in the sense of CH2-H, R~ and R~~ = alkyl), c) a filler comprising alumina flakes.
2. The insulating resin as claimed in claim 1, wherein the ratio of material a) to material b) (in weight/weight) is from >=50:1 to <=300:1.
3. The insulating resin as claimed in claim 1 or 2, wherein the proportion of material a) in the resin (in weight/weight based on glycidyl esters) is from >=0.8:1 to <=1.1.
4. The insulating resin as claimed in any of claims 1 to 3, wherein the proportion of material b) in the resin (in weight/weight based on glycidyl esters) is from >=0.01:1 to <=0.1:1.
5. The insulating resin as claimed in any of claims 1 to 4, wherein component b) is selected from the group comprising 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-isopropylimidazole, imidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-ethylimidazole, imidazole, 1-benzyl-2-phenylimidazole, 1-vinylimidazole, 2-methylimidazole, 2-heptadecylimidazole, 2-phenylimidazole and mixtures thereof.
6. The insulating resin as claimed in any of claims 1 to 5, wherein the d50 of the filler c) is from >=2 µm to <=6 µm.
7. An insulating part comprising an insulating resin as claimed in any of claims 1 to 6.
8. The insulating part as claimed in claim 7, wherein the insulating part is part of a GIL system.
9. The use of a resin system based on glycidyl esters, formed from the starting components comprising:
-11a-a) a material comprising methylnadic anhydride and/or hydrogenated methylnadic anhydride, b) a material comprising an imidazole of the following structure:
where R1 is selected from the group comprising alkyl, long-chain alkyl, alkenyl, cycloalkyl, haloalkyl, aryl;
R2, R3, R4 are each independently selected from the group comprising hydrogen, alkyl, long-chain alkyl, alkenyl, cycloalkyl, haloalkyl, aryl, where one or more nonadjacent CH2 groups in suitable radicals may each independently be replaced by -O-, -S-, -NH-, -NR~-, -SiR~R~~-, -CO-, -COO-, -OCO-, -OCO-O-, CN, -SO2-, -S-CO-, -CO-S-, -CY1=CY2- or -C.ident.C-, specifically in such a way that oxygen and/or sulfur atoms are not bonded directly to one another, and are likewise optionally replaced by aryl or heteroaryl preferably containing 1 to 30 carbon atoms (terminal CH3 groups are understood like CH2 groups in the sense of CH2-H, R~ and R~~ = alkyl) c) a filler comprising alumina flakes as an insulating composition in electrical switchgear.
-11a-a) a material comprising methylnadic anhydride and/or hydrogenated methylnadic anhydride, b) a material comprising an imidazole of the following structure:
where R1 is selected from the group comprising alkyl, long-chain alkyl, alkenyl, cycloalkyl, haloalkyl, aryl;
R2, R3, R4 are each independently selected from the group comprising hydrogen, alkyl, long-chain alkyl, alkenyl, cycloalkyl, haloalkyl, aryl, where one or more nonadjacent CH2 groups in suitable radicals may each independently be replaced by -O-, -S-, -NH-, -NR~-, -SiR~R~~-, -CO-, -COO-, -OCO-, -OCO-O-, CN, -SO2-, -S-CO-, -CO-S-, -CY1=CY2- or -C.ident.C-, specifically in such a way that oxygen and/or sulfur atoms are not bonded directly to one another, and are likewise optionally replaced by aryl or heteroaryl preferably containing 1 to 30 carbon atoms (terminal CH3 groups are understood like CH2 groups in the sense of CH2-H, R~ and R~~ = alkyl) c) a filler comprising alumina flakes as an insulating composition in electrical switchgear.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102009008464A DE102009008464A1 (en) | 2009-02-10 | 2009-02-10 | Cast resin system for insulating materials in switchgear |
| DE102009008464.9 | 2009-02-10 | ||
| PCT/EP2010/050682 WO2010091922A1 (en) | 2009-02-10 | 2010-01-21 | Casting resin system for insulating materials in switch gears |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2751825A1 true CA2751825A1 (en) | 2010-08-19 |
Family
ID=42060632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2751825A Abandoned CA2751825A1 (en) | 2009-02-10 | 2010-01-21 | Casting resin system for insulating materials in switch gears |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US8349937B2 (en) |
| EP (1) | EP2396361A1 (en) |
| KR (1) | KR20110124225A (en) |
| CN (1) | CN102317344A (en) |
| AU (1) | AU2010213031B2 (en) |
| BR (1) | BRPI1008333A2 (en) |
| CA (1) | CA2751825A1 (en) |
| DE (1) | DE102009008464A1 (en) |
| MX (1) | MX2011007853A (en) |
| RU (1) | RU2011137434A (en) |
| UA (1) | UA104751C2 (en) |
| WO (1) | WO2010091922A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102013226705A1 (en) * | 2013-12-19 | 2015-06-25 | Siemens Aktiengesellschaft | Puncture and rollover resistant cast resin composition |
| DE102016205386A1 (en) * | 2016-03-31 | 2017-10-05 | Robert Bosch Gmbh | Hardenable epoxy molding compound |
| UA114768U (en) | 2017-01-30 | 2017-03-10 | SYSTEM OF CONNECTING DETAILS OF THREE-DIMENSIONAL MECHANICAL MODEL | |
| FR3097074B1 (en) * | 2019-06-04 | 2021-10-08 | Nexans | Electrical device comprising a crosslinked layer |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4560716A (en) * | 1983-08-30 | 1985-12-24 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Rust preventing epoxy resin compositions |
| US4559272A (en) | 1984-05-09 | 1985-12-17 | Hughes Aircraft Company | Heat curable polyglycidyl aromatic amine encapsulants |
| DE4434279A1 (en) * | 1994-09-26 | 1996-03-28 | Hoechst Ag | Hardenable, powdery mixtures |
| JPH09208805A (en) * | 1994-11-09 | 1997-08-12 | Nitto Denko Corp | Epoxy resin composition for sealing optical semiconductor device |
| DE69609773T2 (en) * | 1995-06-06 | 2000-12-28 | Nisshin Spinning | Epoxy resin mixture and adhesive based on it |
| DE19523897C2 (en) * | 1995-06-30 | 2002-10-24 | Bosch Gmbh Robert | Use of silicone-modified epoxy resins as casting compounds for electrotechnical or electronic components |
| US6194490B1 (en) | 1998-02-27 | 2001-02-27 | Vantico, Inc. | Curable composition comprising epoxidized natural oils |
| WO2000046317A1 (en) | 1999-02-08 | 2000-08-10 | The Yokohama Rubber Co., Ltd. | Resin compositions |
| US6458472B1 (en) * | 2001-01-08 | 2002-10-01 | Henkel Loctite Corporation | Fluxing underfill compositions |
| CA2561385A1 (en) * | 2004-03-30 | 2005-10-13 | Kaneka Corporation | Hardenable composition |
-
2009
- 2009-02-10 DE DE102009008464A patent/DE102009008464A1/en not_active Withdrawn
-
2010
- 2010-01-21 BR BRPI1008333A patent/BRPI1008333A2/en not_active IP Right Cessation
- 2010-01-21 MX MX2011007853A patent/MX2011007853A/en active IP Right Grant
- 2010-01-21 RU RU2011137434/04A patent/RU2011137434A/en not_active Application Discontinuation
- 2010-01-21 AU AU2010213031A patent/AU2010213031B2/en not_active Ceased
- 2010-01-21 CA CA2751825A patent/CA2751825A1/en not_active Abandoned
- 2010-01-21 UA UAA201109901A patent/UA104751C2/en unknown
- 2010-01-21 US US13/148,721 patent/US8349937B2/en not_active Expired - Fee Related
- 2010-01-21 WO PCT/EP2010/050682 patent/WO2010091922A1/en active Application Filing
- 2010-01-21 CN CN2010800072673A patent/CN102317344A/en active Pending
- 2010-01-21 KR KR1020117018524A patent/KR20110124225A/en not_active Application Discontinuation
- 2010-01-21 EP EP10703174A patent/EP2396361A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| US8349937B2 (en) | 2013-01-08 |
| KR20110124225A (en) | 2011-11-16 |
| AU2010213031A1 (en) | 2011-08-11 |
| CN102317344A (en) | 2012-01-11 |
| DE102009008464A1 (en) | 2010-08-12 |
| WO2010091922A1 (en) | 2010-08-19 |
| EP2396361A1 (en) | 2011-12-21 |
| RU2011137434A (en) | 2013-03-20 |
| MX2011007853A (en) | 2011-08-15 |
| UA104751C2 (en) | 2014-03-11 |
| BRPI1008333A2 (en) | 2016-02-23 |
| AU2010213031B2 (en) | 2013-02-07 |
| US20110313103A1 (en) | 2011-12-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |
Effective date: 20160121 |